US3442931A - Preparation of 2,2-disubstituted-1,3-propanediol monoesters - Google Patents
Preparation of 2,2-disubstituted-1,3-propanediol monoesters Download PDFInfo
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- US3442931A US3442931A US463298A US3442931DA US3442931A US 3442931 A US3442931 A US 3442931A US 463298 A US463298 A US 463298A US 3442931D A US3442931D A US 3442931DA US 3442931 A US3442931 A US 3442931A
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- Prior art keywords
- cyclohexene
- formaldehyde
- catalyst
- reaction
- carboxaldehyde
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- -1 2,2-disubstituted-1,3-propanediol Chemical class 0.000 title description 24
- 238000002360 preparation method Methods 0.000 title description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 91
- 239000003054 catalyst Substances 0.000 description 31
- 235000019256 formaldehyde Nutrition 0.000 description 30
- 238000000034 method Methods 0.000 description 30
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 26
- 150000001299 aldehydes Chemical class 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 150000001340 alkali metals Chemical class 0.000 description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 14
- 150000001342 alkaline earth metals Chemical class 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 11
- 150000007514 bases Chemical class 0.000 description 11
- 150000004703 alkoxides Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000013638 trimer Substances 0.000 description 8
- HNWHVVWRJAXEEC-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 2-methylpropanoate Chemical compound CC(C)C(=O)OCC(C)(C)CO HNWHVVWRJAXEEC-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002837 carbocyclic group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- DCFDVJPDXYGCOK-UHFFFAOYSA-N cyclohex-3-ene-1-carbaldehyde Chemical compound O=CC1CCC=CC1 DCFDVJPDXYGCOK-UHFFFAOYSA-N 0.000 description 3
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 2
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 2
- DMNPATRDUSBTAD-UHFFFAOYSA-N 2-ethoxycyclohex-3-ene-1-carbaldehyde Chemical compound CCOC1C=CCCC1C=O DMNPATRDUSBTAD-UHFFFAOYSA-N 0.000 description 2
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 2
- ABAHVCWRMOPYKP-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1=CCCC(C=O)C1 ABAHVCWRMOPYKP-UHFFFAOYSA-N 0.000 description 2
- YPHGCKOZJCGDTF-UHFFFAOYSA-N 4-methylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1=CCC(C=O)CC1 YPHGCKOZJCGDTF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- VUSWCWPCANWBFG-UHFFFAOYSA-N cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1 VUSWCWPCANWBFG-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000020030 perry Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000001893 (2R)-2-methylbutanal Substances 0.000 description 1
- BHVGMUDWABJNRC-UHFFFAOYSA-N (±)-2-methylhexanal Chemical compound CCCCC(C)C=O BHVGMUDWABJNRC-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- BUAKPITZELZWNI-UHFFFAOYSA-N 1-chlorocyclohexene Chemical compound ClC1=CCCCC1 BUAKPITZELZWNI-UHFFFAOYSA-N 0.000 description 1
- RACNVJFSQSOKGQ-UHFFFAOYSA-N 2-butylhexanal Chemical compound CCCCC(C=O)CCCC RACNVJFSQSOKGQ-UHFFFAOYSA-N 0.000 description 1
- RASFNDNSLQUKNY-UHFFFAOYSA-N 2-ethyl-4-methylpentanal Chemical compound CCC(C=O)CC(C)C RASFNDNSLQUKNY-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- OZGRFPZYTKHWMZ-UHFFFAOYSA-N 2-ethylpentanal Chemical compound CCCC(CC)C=O OZGRFPZYTKHWMZ-UHFFFAOYSA-N 0.000 description 1
- IREORVYCKDQFMD-UHFFFAOYSA-N 2-propylhexanal Chemical compound CCCCC(C=O)CCC IREORVYCKDQFMD-UHFFFAOYSA-N 0.000 description 1
- BAUHZKXBGXCLBO-UHFFFAOYSA-N 2-propylpentanal Chemical compound CCCC(C=O)CCC BAUHZKXBGXCLBO-UHFFFAOYSA-N 0.000 description 1
- SECSYNMYFTVLOQ-UHFFFAOYSA-N 4-ethylcyclohex-3-ene-1-carbaldehyde Chemical compound CCC1=CCC(C=O)CC1 SECSYNMYFTVLOQ-UHFFFAOYSA-N 0.000 description 1
- CFOHRCNONSEVOJ-UHFFFAOYSA-N 4-ethylcyclohexene Chemical compound CCC1CCC=CC1 CFOHRCNONSEVOJ-UHFFFAOYSA-N 0.000 description 1
- KYXMUABTWXREOG-UHFFFAOYSA-N 5-methylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1CC(C=O)CC=C1 KYXMUABTWXREOG-UHFFFAOYSA-N 0.000 description 1
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- BOPCAWBPVSVBMM-UHFFFAOYSA-N 6-methylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1CC=CCC1C=O BOPCAWBPVSVBMM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108091092920 SmY RNA Proteins 0.000 description 1
- 241001237710 Smyrna Species 0.000 description 1
- JTRLVVUONAUOHI-UHFFFAOYSA-N [1-(hydroxymethyl)-4-methylcyclohex-3-en-1-yl]methanol Chemical compound CC1=CCC(CO)(CO)CC1 JTRLVVUONAUOHI-UHFFFAOYSA-N 0.000 description 1
- YXEBFFWTZWGHEY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohex-3-en-1-yl]methanol Chemical compound OCC1(CO)CCC=CC1 YXEBFFWTZWGHEY-UHFFFAOYSA-N 0.000 description 1
- HLIOCTNQCNHHRB-UHFFFAOYSA-N [2-ethyl-2-(hydroxymethyl)hexyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(CC)(CO)CCCC HLIOCTNQCNHHRB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- DADHEABVOGEWRV-UHFFFAOYSA-N aluminum magnesium ethanolate Chemical compound [Mg++].[Al+3].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] DADHEABVOGEWRV-UHFFFAOYSA-N 0.000 description 1
- JTXLLJGEKOMTDQ-UHFFFAOYSA-N aluminum sodium methanolate Chemical compound C[O-].C[O-].C[O-].C[O-].[Al+3].[Na+] JTXLLJGEKOMTDQ-UHFFFAOYSA-N 0.000 description 1
- JTQBAFGYSGLZOO-UHFFFAOYSA-N aluminum;calcium;propan-2-olate Chemical compound [Al+3].[Ca+2].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] JTQBAFGYSGLZOO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- MMLSWLZTJDJYJH-UHFFFAOYSA-N calcium;propan-2-olate Chemical compound [Ca+2].CC(C)[O-].CC(C)[O-] MMLSWLZTJDJYJH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- IPUNVLFESXFVFH-UHFFFAOYSA-N methyl cyclohex-3-ene-1-carboxylate Chemical compound COC(=O)C1CCC=CC1 IPUNVLFESXFVFH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CBMSDILKECEMOT-UHFFFAOYSA-N potassium;2-methylpropan-1-olate Chemical compound [K+].CC(C)C[O-] CBMSDILKECEMOT-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GJIMNMWWEUBESO-UHFFFAOYSA-M sodium formaldehyde hydroxide Chemical compound [OH-].[Na+].O=C GJIMNMWWEUBESO-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- This invention relates to a novel chemical process and more particularly to a novel process for preparing certain 2,2-disubstituted-1,3-propanediol monoesters.
- the 2,2-disubstituted-1,3-propanediol monoesters are prepared in accordance with the process of the invention by condensing one mole of formalydehyde with two moles of an aldehyde having only one a-hydrogen atom.
- the process of our invention thus involves a mixed, trimeric aldehyde condensation and depends, in part, upon our discovery that formaldehyde and aldehydes having only one a-hydrogen atom, when contacted with a strongly basic catalyst at a temperature below 50 C., unexpectedly form a mixed aldehyde trimer, i.e., a 2,2-disubstituted-1,3-propanediol monoester.
- each of R and R when taken singly is alkyl and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
- the catalysts which are useful in the process of our invention are strongly basic compounds containing an alkali metal or an alkaline earth metal.
- the useful basic catalysts are the alkoxides, hydroxides, carbonates, etc. of alkali metals or alkaline earth metals.
- an alkoxide is employed as the catalyst, it is essential that the reaction be carried out under substantially anhydrous conditions whereas, when the catalyst is a hydroxide or a carbonate, aqueous solutions of the catalysts are generally employed.
- FIGURE 1 is a schematic flow diagram of a continuous embodiment of our process in which isobutyraldehyde is contacted with formaldehyde in the presence of sodium ethoxide to form neopentyl glycol monoisobutyrate, i.e., 2,2-dimethyl-1,3-propanediol, isobutyrate.
- isobutyraldehyde, and formaldehyde are introduced into circulating line 4 via lines 1 and 2, respectively.
- Sodium ethoxide e.g., an ethanol solution of sodium ethoxide
- circulating line 4 via line 3
- the mixture containing isobutyraldehyde, formaldehyde and sodium ethoxide is [forced by pump 5 through heat exchanger 6 and into reactor 8 via conduit 7.
- Heat exchanger 6 maintains the reaction temperature at below 50 C.
- the mixture is directed out of conduit 7 to splash against the top of reactor 8 to insure thorough mixing of the isobutyraldehyde, the formaldehyde and the sodium ethoxide.
- a portion of the reaction mixture is withdrawn through line 4 and recirculated through pump 5.
- the remainder of the reaction mixture is withdrawn via line 11 and passed into mixing tank 12.
- Water is introduced into tank 12 via line 13 and the water and reaction mixture are thoroughly mixed in order to decompose the sodium ethoxide.
- the mixture of water and crude reaction product is withdrawn from tank 12 via line 14 and passed to decanter 15.
- Water is removed from the bottom of decanter 15 and discarded via line 16 and the crude reaction product is overflowed from decanter 15 via line 17 to distillation column 20.
- Uureacted isobutyraldehyde is removed overhead from distillation column 20 and recycled to line 4 via line 18.
- Neopentyl glycol isobutyrate is removed from the base of column 20 via line 19. The neopentyl glycol isobutyrate can be further purified by additional distillation, if necessary.
- FIGURE 2 is a schematic flow diagram of a continuous embodiment of our process in which isobutyraldehyde is contacted with formaldehyde in the presence of an aqueous solution of sodium hydroxide to form neopentyl glycol monoisobutyrate.
- isobutyraldehyde and formaldehyde are introduced into circulating line 24 via lines 21 and 22.
- Sodium hydroxide e.g., an aqueous solution of sodium hydroxide is introduced into line 24 via line 23 and the mixture of isobutyraldehyde, formaldehyde and sodium hydroxide is forced by pump 25 through heat exchanger 26.
- Heat exchanger 26 maintains the reaction mixture at a temperature below about 50 C.
- the mixture passes upward through conduit 27 and splashes against the top of reactor 28 with sufficient force to insure that the reactants and catalyst are thoroughly mixed.
- the reaction mixture is withdrawn from reactor 28 via line 31 and passed to decanter 32.
- the aqueous phase, which is separated in decanter 32, is removed via line 33.
- a portion of the aqueous phase is recycled to circulating line 24 via line 34 and the remainder is discarded via line 35.
- the water soluble salts of organic acids which are formed during the course of the reaction inhibit the formation of the desired mixed aldehyde trimer and should not be allowed to build up in the aqueous phase which is recycled.
- the rate at which the aqueous phase is discarded via line 35 is usually determined by the concentration of Water soluble organic salts in the aqueous phase and should be sufficiently high to maintain the concentration of salts in the aqueous phase at less than 10% and preferably at less than 5% by weight.
- the organic phase separated in decanter 32 is passed to distillation column 37 via line 36.
- Isobutyraldehyde is removed overhead from distillation column 37 and recycled to circulating line 4 via line 38.
- Neopentyl glycol monoisobutyrate, removed from the base of column 37 by line 39 can be further purified, e.g., by further distillation, if desired.
- mixed aldehyde trimers can be formed by contacting formaldehyde with an aldehyde having only one tit-hydrogen atom in the presence of a strongly basic catalyst at a temperature below about 50 C.
- a predominant amount of the mixed aldehyde trimer i.e., the 2,2-disubstituted-l,3-propanediol monoester and only a minor amount of the trimer of the aldehyde having only one a-hydro gen atom.
- the process of our invention is carried out by contacting formaldehyde with an aldehyde having only one a-hydrogen atom in the presence of a strongly basic compound as a catalyst.
- the strongly basic compounds which are useful are generally compounds containing an alkali or an alkaline earth metal.
- the useful basic catalysts are compounds such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, lithium hydroxide, lithium carbonate, calcium hydroxide, magnesium hydroxide, lithium methoxide, sodium ethoxide, potassium isobutoxide, sodium methoxide, magnesium ethoxide, calcium isopropoxide, etc.
- Included among the useful alkoxide catalysts are complex metallic alkoxides such as magnesium aluminum ethoxide, calcium aluminum isopropoxide, sodium aluminum methoxide, etc.
- the catalyst concentration in the reaction zone is generally maintained from about 0.005 to about 5 moles of alkali metal or alkaline earth metal per liter of reaction zone.
- concentration of the alkali metal or alkaline earth metal is maintained at about 0.005 to about 5 moles per liter of reactor volume. If the reactor vessel is only partially filled, the concentration of the alkali metal or alkaline earth metal is maintained at about 0.005 to about 5 moles per liter within the portion of the reactor which is filled.
- the reaction zone contains two liquid phases, i.e., an organic phase and an aqueous phase.
- the volume ratio of organic phase to aqueous phase is generally from about 90:10 to about 50:50 and is preferably from about 85:15 to about 75:25. Since substantially all of the basic catalyst present within the reaction zone is in the aqueous phase, the concentration of basic compound in the aqueous phase is necessarily higher than the average concentration within the reaction zone and generally ranges from about 0.01 molar up to the concentration of a saturated solution, e.g., about molar at 0 C. for sodium hydroxide. The aqueous phase and organic phase must be intimately contacted with each other.
- the necessary intimate contacting can be accomplished by agitating or stirring the reaction mixture or, when the process is carried out continuously, by pumping the reaction mixture into the reactor at high velocity.
- the formaldehyde can be introduced into the reaction zone as an aqueous solution or as a slurry of paraldehyde in the aldehyde having a single tat-hydrogen atom.
- Particularly preferred as basic catalysts when aqueous solutions are employed are the alkali metal and alkaline earth metal hydroxides.
- the reaction medium be substantially anhydrous in order to avoid decomposition of the alkoxide catalyst.
- the formaldehyde can be introduced into the reaction zone as a slurry of parafonmaldehyde in the aldehyde having a single tit-hydrogen atom or as a solution in an inert solvent, e.g., an alkanol such as methanol, ethanol, etc.
- the preferred alkoxides for use as catalysts in the process of our invention are those prepared from alkanols having up to about 12 carbon atoms.
- Especially preferred alkoxides are those from lower alkanols, e.g., alkanols of up to about 4 carbon atoms.
- the reactants and catalysts are contacted at temperatures below about 50 C. At higher temperatures, there is a pronounced tendency for the aldehyde having a single a-hydrogen atom to react with itself to form products other than the desired mixed trimer. Preferred reaction temperatures are below about 30 C.
- the process of our invention involves the reaction of one mole of formaldehyde with two moles of an aldehyde having a single a-hydrogen atom.
- a stoichiometric excess of either formaldehyde or the aldehyde having a single ot-hydrogen atom can be employed in accordance with the process of our invention.
- aldehydes having a single a-hydrogen atom which are useful in the process of our invention are compounds such as isobutyraldehyde, 2-methylbutyraldehyde, 2 ethylbutyraldehyde, Z-methylpentaldehyde, 2-ethylpentaldehyde, 2-propylpentaldehyde, 2-methylhexaldehyde, Z-ethylhexaldehyde, 2-propylhexaldehyde, 2- butylhexaldehyde, 3-cyclohexene-l-carboxaldehyde, 2- rnethy1-3-cyclohexene-l-carboxaldehyde, 3-methyl-3-cyclohexene-l-carboxaldehyde, 4-methyl-3-cyclohexene-l-carboxaldehyde, 5-methyl-3-cyclohexene-l-carboxaldehyde, or 6-
- 2-ethylhexanal is reacted with formaldehyde, as described in Example 1, to yield 2-ethyl-2-butyl-3-hydroxypropyl 2-ethylhexanoate.
- reaction product was washed to remove the catalyst and the glycol monoester subsequently distilled yielding a mixture of 1,1-dihydroxy-3-methyl-cyclohexene 3-methyl 3 cyclohexene 1 carboxylate; 1,1 dihydroxymethyl 3 methyl 3 cyclohexene 4 methyl 3 cyclohexene 1 carboxylate; 1,1 dihydroxymethyl 4 methyl 3 cyclohexene 3 methyl 3 cyclohexene- 1 carboxylate; and 1,1 dihydroxymethyl 4 methyl-3-cyclohexene 4 methyl-3-cyclohexene-l-carboxylate in 72% yield.
- each of R and R when taken singly, is alkyl of up to about 8 carbon atoms and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
- each of R and R when taken singly, is alkyl of up to about 8 carbon atoms, and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
- each of R and R when taken singly, is alkyl of up to about 8 carbon atoms and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
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Description
May 6, 1969 R. a. DUKE, JR, T 3,442,931
PREPARATION OF 2,2DISUBSTITUTED-l,5-PROPANEDIOL MONOESTERS Fild June 11. 1965 RECYCLE ISOBUTYRALDEHYDE -20 ISOBUTYRALDEHYDE I6 FORMALDEHYDE SODIUM HYDROXIDE WATER s NEOPENTYL GLYCOL ISOBUTYRATE RECYCLE ISOBUTYRALDEHYDE ISOBUTYRALDEHYD FORMALDEHYDE NEOPENTYL GLYCOL SODIUM HYDROXIDQ ISOBUTYRATE 23 ROY B- DUKE, JR- MILTON A- PERRY W INVENTORS cue WATER ATTORNEYS United States Patent C 3,442,931 PREPARATION OF 2,2-DISUBSTlTUTED-1,3- PROPANEDIOL MONOESTERS Roy B. Duke, Jr., Smyrna, Ga., and Milton A. Perry,
Longview, Tex., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed June 11, 1965, Ser. No. 463,298
Int. Cl. C07c 67/00 US. Cl. 260-468 Claims ABSTRACT OF THE DISCLOSURE A process for the preparation of 2,2-disubstituted-l,3- propanediol monoesters by condensing formaldehyde with an aldehyde having only one alpha-hydrogen atom in a 1:2 mole ratio in the presence of a strongly basic catalyst at temperatures below 50 C. The products of the process are well-known and valuable articles of commerce, for example, as intermediates in the production plasticizers.
This invention relates to a novel chemical process and more particularly to a novel process for preparing certain 2,2-disubstituted-1,3-propanediol monoesters.
The 2,2-disubstituted-1,3-propanediol monoesters are prepared in accordance with the process of the invention by condensing one mole of formalydehyde with two moles of an aldehyde having only one a-hydrogen atom. The process of our invention thus involves a mixed, trimeric aldehyde condensation and depends, in part, upon our discovery that formaldehyde and aldehydes having only one a-hydrogen atom, when contacted with a strongly basic catalyst at a temperature below 50 C., unexpectedly form a mixed aldehyde trimer, i.e., a 2,2-disubstituted-1,3-propanediol monoester.
The process of our invention can be illustrated by the following equation, showing the use of certain preferred reactants.
In the formulae of the above equation, each of R and R when taken singly, is alkyl and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
The catalysts which are useful in the process of our invention are strongly basic compounds containing an alkali metal or an alkaline earth metal. Among the useful basic catalysts are the alkoxides, hydroxides, carbonates, etc. of alkali metals or alkaline earth metals. When an alkoxide is employed as the catalyst, it is essential that the reaction be carried out under substantially anhydrous conditions whereas, when the catalyst is a hydroxide or a carbonate, aqueous solutions of the catalysts are generally employed.
FIGURE 1 is a schematic flow diagram of a continuous embodiment of our process in which isobutyraldehyde is contacted with formaldehyde in the presence of sodium ethoxide to form neopentyl glycol monoisobutyrate, i.e., 2,2-dimethyl-1,3-propanediol, isobutyrate. Referring to FIGURE 1, isobutyraldehyde, and formaldehyde are introduced into circulating line 4 via lines 1 and 2, respectively. Sodium ethoxide, e.g., an ethanol solution of sodium ethoxide, is introduced into circulating line 4 via line 3 and the mixture containing isobutyraldehyde, formaldehyde and sodium ethoxide is [forced by pump 5 through heat exchanger 6 and into reactor 8 via conduit 7. Heat exchanger 6 maintains the reaction temperature at below 50 C. The mixture is directed out of conduit 7 to splash against the top of reactor 8 to insure thorough mixing of the isobutyraldehyde, the formaldehyde and the sodium ethoxide. A portion of the reaction mixture is withdrawn through line 4 and recirculated through pump 5. The remainder of the reaction mixture is withdrawn via line 11 and passed into mixing tank 12. Water is introduced into tank 12 via line 13 and the water and reaction mixture are thoroughly mixed in order to decompose the sodium ethoxide. The mixture of water and crude reaction product is withdrawn from tank 12 via line 14 and passed to decanter 15. Water is removed from the bottom of decanter 15 and discarded via line 16 and the crude reaction product is overflowed from decanter 15 via line 17 to distillation column 20. Uureacted isobutyraldehyde is removed overhead from distillation column 20 and recycled to line 4 via line 18. Neopentyl glycol isobutyrate is removed from the base of column 20 via line 19. The neopentyl glycol isobutyrate can be further purified by additional distillation, if necessary.
FIGURE 2 is a schematic flow diagram of a continuous embodiment of our process in which isobutyraldehyde is contacted with formaldehyde in the presence of an aqueous solution of sodium hydroxide to form neopentyl glycol monoisobutyrate. Referring to FIGURE 2, isobutyraldehyde and formaldehyde are introduced into circulating line 24 via lines 21 and 22. Sodium hydroxide, e.g., an aqueous solution of sodium hydroxide is introduced into line 24 via line 23 and the mixture of isobutyraldehyde, formaldehyde and sodium hydroxide is forced by pump 25 through heat exchanger 26. Heat exchanger 26 maintains the reaction mixture at a temperature below about 50 C. The mixture passes upward through conduit 27 and splashes against the top of reactor 28 with sufficient force to insure that the reactants and catalyst are thoroughly mixed. The reaction mixture is withdrawn from reactor 28 via line 31 and passed to decanter 32. The aqueous phase, which is separated in decanter 32, is removed via line 33. A portion of the aqueous phase is recycled to circulating line 24 via line 34 and the remainder is discarded via line 35. The water soluble salts of organic acids which are formed during the course of the reaction inhibit the formation of the desired mixed aldehyde trimer and should not be allowed to build up in the aqueous phase which is recycled. The rate at which the aqueous phase is discarded via line 35 is usually determined by the concentration of Water soluble organic salts in the aqueous phase and should be sufficiently high to maintain the concentration of salts in the aqueous phase at less than 10% and preferably at less than 5% by weight. The organic phase separated in decanter 32 is passed to distillation column 37 via line 36. Isobutyraldehyde is removed overhead from distillation column 37 and recycled to circulating line 4 via line 38. Neopentyl glycol monoisobutyrate, removed from the base of column 37 by line 39 can be further purified, e.g., by further distillation, if desired.
Valuable processes for the production of glycol monoesters by the trimeric condensation of aldehydes having a single a-hydrogen atom are described in US. Patent 3,091,632 to Hagemeyer and Wright and in copending United States patent application Ser. No. 321,135 of Perry and Hagemeyer, filed Nov. 4, 1963. The processes described in the above patent and application are however for the production of trimers of a single aldehyde and do not relate to the production of mixed aldehyde trimers.
We have now unexpectedly discovered that mixed aldehyde trimers can be formed by contacting formaldehyde with an aldehyde having only one tit-hydrogen atom in the presence of a strongly basic catalyst at a temperature below about 50 C. In accordance with the process of our invention we unexpectedly obtain a predominant amount of the mixed aldehyde trimer, i.e., the 2,2-disubstituted-l,3-propanediol monoester and only a minor amount of the trimer of the aldehyde having only one a-hydro gen atom.
As pointed out hereinbefore, the process of our invention is carried out by contacting formaldehyde with an aldehyde having only one a-hydrogen atom in the presence of a strongly basic compound as a catalyst. The strongly basic compounds which are useful are generally compounds containing an alkali or an alkaline earth metal. Among the useful basic catalysts are compounds such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, lithium hydroxide, lithium carbonate, calcium hydroxide, magnesium hydroxide, lithium methoxide, sodium ethoxide, potassium isobutoxide, sodium methoxide, magnesium ethoxide, calcium isopropoxide, etc. Included among the useful alkoxide catalysts are complex metallic alkoxides such as magnesium aluminum ethoxide, calcium aluminum isopropoxide, sodium aluminum methoxide, etc.
The catalyst concentration in the reaction zone is generally maintained from about 0.005 to about 5 moles of alkali metal or alkaline earth metal per liter of reaction zone. Thus, when the reaction vessel in which the process of our invention is completely filled, the concentration of the alkali metal or alkaline earth metal is maintained at about 0.005 to about 5 moles per liter of reactor volume. If the reactor vessel is only partially filled, the concentration of the alkali metal or alkaline earth metal is maintained at about 0.005 to about 5 moles per liter within the portion of the reactor which is filled.
When the process of our invention is carried out with the catalyst dissolved in water, the reaction zone contains two liquid phases, i.e., an organic phase and an aqueous phase. The volume ratio of organic phase to aqueous phase is generally from about 90:10 to about 50:50 and is preferably from about 85:15 to about 75:25. Since substantially all of the basic catalyst present within the reaction zone is in the aqueous phase, the concentration of basic compound in the aqueous phase is necessarily higher than the average concentration within the reaction zone and generally ranges from about 0.01 molar up to the concentration of a saturated solution, e.g., about molar at 0 C. for sodium hydroxide. The aqueous phase and organic phase must be intimately contacted with each other. The necessary intimate contacting can be accomplished by agitating or stirring the reaction mixture or, when the process is carried out continuously, by pumping the reaction mixture into the reactor at high velocity. The formaldehyde can be introduced into the reaction zone as an aqueous solution or as a slurry of paraldehyde in the aldehyde having a single tat-hydrogen atom. Particularly preferred as basic catalysts when aqueous solutions are employed are the alkali metal and alkaline earth metal hydroxides.
When an alkoxide is employed as catalyst in the process of our invention, it is essential that the reaction medium be substantially anhydrous in order to avoid decomposition of the alkoxide catalyst. The formaldehyde can be introduced into the reaction zone as a slurry of parafonmaldehyde in the aldehyde having a single tit-hydrogen atom or as a solution in an inert solvent, e.g., an alkanol such as methanol, ethanol, etc. The preferred alkoxides for use as catalysts in the process of our invention are those prepared from alkanols having up to about 12 carbon atoms. Especially preferred alkoxides are those from lower alkanols, e.g., alkanols of up to about 4 carbon atoms.
The reactants and catalysts are contacted at temperatures below about 50 C. At higher temperatures, there is a pronounced tendency for the aldehyde having a single a-hydrogen atom to react with itself to form products other than the desired mixed trimer. Preferred reaction temperatures are below about 30 C.
As pointed out hereinbefore, the process of our invention involves the reaction of one mole of formaldehyde with two moles of an aldehyde having a single a-hydrogen atom. A stoichiometric excess of either formaldehyde or the aldehyde having a single ot-hydrogen atom can be employed in accordance with the process of our invention. However, for reasons of economy, it is generally preferred to employ stoichiometric equivalents of the reactants.
Among the aldehydes having a single a-hydrogen atom which are useful in the process of our invention are compounds such as isobutyraldehyde, 2-methylbutyraldehyde, 2 ethylbutyraldehyde, Z-methylpentaldehyde, 2-ethylpentaldehyde, 2-propylpentaldehyde, 2-methylhexaldehyde, Z-ethylhexaldehyde, 2-propylhexaldehyde, 2- butylhexaldehyde, 3-cyclohexene-l-carboxaldehyde, 2- rnethy1-3-cyclohexene-l-carboxaldehyde, 3-methyl-3-cyclohexene-l-carboxaldehyde, 4-methyl-3-cyclohexene-l-carboxaldehyde, 5-methyl-3-cyclohexene-l-carboxaldehyde, or 6-methyl-3-cyclohexene-l-carboxaldehyde, 2-ethyl-3- cyclohexene-l-carboxaldehyde, 3-ethyl-3-cyclohexene-lcarboxaldehyde, 4-ethyl-3-cyclohexene-l-carboxaldehyde, 5-ethyl-3-cyclohexene-l-carboxaldehyde, or 6-ethyl-3-cyclohexene l-carboxaldehyde, 3-chloro-3-cyclohexene-lcarboxaldehyde, and/or 4-chloro-3-cyclohexene-l-carboxaldehyde, 2-ethoxy-3-cyclohexene-l-carboxaldehyde, etc.
The following examples illustrates the process of the invention.
2-ethylhexanal is reacted with formaldehyde, as described in Example 1, to yield 2-ethyl-2-butyl-3-hydroxypropyl 2-ethylhexanoate.
EXAMPLE 3 C H: C2115 A: N30 0 H3 2CH3- H-CHz-CH-CHO HCHO C 2H5 I? CzIIs (3H3 ITO-CH2- I H2OC- H-CHz-C H (3H2 Olly-C II-C II;
5 Z-ethylisohexanal is reacted with formaldehyde, as described in Example 1, to yield 2-ethyl-2-is-obutyl-3-hydroxypropyl Z-ethylisohexanoate.
Isobutyraldehyde is reacted with formaldehyde, as described in Example '1, yield-ing hydroxyne-opentyl isobutyrate.
EXAMPLE 5 CzHs 2H5 2-ethylbutyraldehyde is reacted with formaldehyde, as described in Example 1, to yield 2,-2-diethyl-3-hydroxypropyl-Z-ethylbutyrate.
EXAMPLE 6 CH; 6 NaOCHa 2C2Hr- H-CHO HCHO (EH; CH3 HO-CHa-C-CHz-U-C-JH-CzH;
Z-methylbutyraldehyde was reacted with formaldehyde as described in Example 1, yielding 2-methyl-2-ethyl-3- hydroxypropyl Z-methylbutyrate.
EXAMPLE 7 II HO-C H, cHi-oo-O 3-cyclohexene-1-carboxaldehyde (2 moles), formed by the reaction of butadiene with acrolein, was added to an anhydrous methanolic solution of formaldehyde containing sodium methoxide as catalyst. The temperature was controlled between 0' C. and 30 C. during a 4-hour reaction period. The reaction product was washed to remove the catalyst and subsequently distilled yielding, 1,1-dihydroxymethyl-3-cyclohexene 3-cycl0l1ex-,
ene-l-carboxylate (78% EXAMPLE '8 CH1 NSOCZHE HCHO o l HO-CE: CH2O CH3 Ha 6-methyl-3-cyclohexene-Z-carboxaldehyde (2 moles), formed by the Diels-Alder condensation of butadiene with crotonaldehyde, was added to an anhydrous ethanolic solution of formaldehyde (1 mole) containing 5% sodium ethoxide as catalyst. The temperature was controlled between 0 C. and 30 C. during a 6-hour reaction period. The reaction product was Washed with water to yield 1,1 dihydroxymethyl 6 methyl 3 cyclohexene 6-methyl-3 -cyclohexene-1-carboxylate (72% EXAMPLE '9 CH0 10 021350 NaOCHa 2 ECHO CzHs 2-ethoxy-3-cyclohexene-l-carboxaldehyde, formed by the reaction of l-ethoxy butadiene and acrolein (2 moles); was added to anhydrous methanolic formaldehyde (1 mole) containing 5% sodium methoxide catalyst. The
temperature was controlled between 0 C. and C. during a reaction period of 6 hours. The reaction product was subsequently washed with water to remove the catalyst and then distilled yielding 1,1-dihydroxymethyl-2- 30 ethoxy 3 cyclohexene 2 eth-oxy 3 cyclohexene 1- car-boxylate 69 EXAMPLE 1O CHO C Cl KOCiHt g HCHO BIO-CH2 GHQ-Q- A mixture of 3-chloro-3-eyclohexene-1-carboxaldehyde and 4-chloro-3-cyclohexene l-carboxaldehyde (2 moles), formed by the Diels-Alder condensation of 2-chlorobutadiene (chloroprene) with acrolein, was added to an anhydrous alcoholic solution of formaldehyde containing 5% potassium tertiary butoxidc as catalyst. The temperature was controlled between 0 C. and
30 C. during an 8-hour period. The reaction product was washed with water to remove the catalyst and the glycol monoester subsequently distilled yielding a mixture of 1 ,'1 dihydroxymethyl 3 chloro 3 cyclohexene 3-chloro-3-cyclohexene-l-carboxylate; 1,1-dihydroxymethyl-3-chloro-3-cyclohexene 4-chloro-3-cyclohexene-lcarboxylate; 1,1 dihydroxymethyl 4 chloro 3 cyclohexene 3-chloro-3-cyclohexene-l-carboxylate; and 1,1- dihydr-oxymethyl 4 chl-oro 3 cyclohexene 4 chloro- 0 3-cyclohexene-l-carboxylate in 62% yield.
EXAMPLE 11 0110 (I) OH:
A mixture of 3-methyl-3-cyclohexene-l-carboxaldehyde and 4-methyl-3-cyclohexen-l-carboxaldehyde (2 moles), formed by the Diels-Alder condensation of iso- 7 prene with acrolein, was added to an alcoholic solution 7 of formaldehyde (1 mole) containing sodium ethoxide as catalyst. The temperature was controlled between 0 C. and 50 C. during a 4-hour reaction period. The reaction product was washed to remove the catalyst and the glycol monoester subsequently distilled yielding a mixture of 1,1-dihydroxy-3-methyl-cyclohexene 3-methyl 3 cyclohexene 1 carboxylate; 1,1 dihydroxymethyl 3 methyl 3 cyclohexene 4 methyl 3 cyclohexene 1 carboxylate; 1,1 dihydroxymethyl 4 methyl 3 cyclohexene 3 methyl 3 cyclohexene- 1 carboxylate; and 1,1 dihydroxymethyl 4 methyl-3-cyclohexene 4 methyl-3-cyclohexene-l-carboxylate in 72% yield.
As can be seen, we have provided a process involving a novel combination of reactants, reaction conditions and catalysts which unexpectedly produce certain 2,2-disubstituted-1,3-propanediol monoesters in yields exceeding about 50 percent.
Although the invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, it will be understoood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. The process which comprises contacting formaldehyde with an aldehyde of the formula:
l IU-CH-CHO in a 1:2 mole ratio in the presence of a dissolved basic catalyst at a temperature below about 50 C. and obtaining a glycol mouoester of the formula:
32 R1-('IHCHO in a 1:2 mole ratio in the presence of a dissolved basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below about 50 C. and obtaining a glycol monoester of the formula:
wherein each of R and R when taken singly, is alkyl of up to about 8 carbon atoms and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
4. The process which comprises contacting formaldehyde with an aldehyde of the formula:
in the presence of an aqueous solution of a basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below about 50 C. and containing a glycol monoester of the formula:
wherein each of R and R when taken singly, is alkyl of up to about 8 carbon atoms, and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
5. The process which comprises contacting formaldehyde with an aldehyde of the formula:
in a 1:2 mole ratio in the presence of a solution of an alkoxide of a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below about 50 C. and obtaining a glycol monoester of the formula:
wherein each of R and R when taken singly, is alkyl of up to about 8 carbon atoms and R and R when taken collectively with the carbon atom to which they are attached, represent an aliphatic carbocyclic group having 6 ring carbon atoms.
6. The process which comprises contacting formaldehyde with isobutyraldehy'de in a 1:2 mole ratio in the presence of a dissolved basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below about 30 C. and obtaining neopentyl glycol monoisobutyrate.
7. The process which comprises contacting formaldehyde with Z-ethylhexanal in a 1:2 mole ratio in the presence of a dissolved basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below about 30 C. and obtaining 2-ethyl-2-butyl-3-hydroxypropyl Z-ethylhexanoate.
8. The process which comprises contacting formaldehyde with 2-ethylisohexanal in a 1:2 mole ratio in the presence of a dissolved basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below 30 C. and obtaining 2-ethyl-2-isobutyl-3-hydroxypropyl 2-ethyl isohexanoate.
9. The process which comprises contacting formaldehyde with 2-methylpentanal in a 1:2 mole ratio in the presence of a dissolved basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b) alkaline earth metals at a temperature below about 30 C.and obtaining 2-methyl-2-propyl 3-hydroxypropyl Z-methyl pentanoate.
10. The process which comprises contacting formaldehyde with 3-cyclohexene-l-carboxaldehyde in a 1:2- mole ratio in the presence of a dissolved basic compound containing a metal selected from the group consisting of: (a) alkali metals, and (b)' alkaline earth metals at a temperature below about 30 C. and obtaining 1,1-dihydroxymethyl-3-cyclohexane 3-cyclohexene-1-carboxylate.
References Cited Wessely: Monatsh. Fur Chemie, vol. 21, pp. 216-234 (1900).
US. Cl. X.R. 260-494, 598
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